JPH01315460A - Molding material of polycarbonate resin - Google Patents

Abstract

PURPOSE:To obtain a molding material of polycarbonate resin suitable as an optical molding material, having excellent moldability, especially excellent mold release characteristics, mold transcription, heat resistance, slight reduction in molecular weight and a little discoloration, by blending a polycarbonate with a specific amount of a specific alpha-monoalkylglyceryl ether. CONSTITUTION:100 pts.wt. aromatic polycarbonate is blended with 0.001-0.5 pts.wt. alpha-monoalkylglyceryl ether (e.g., n-octylglyceryl ether or n-decylglyceryl ether) shown by the formula (R is 8-22C saturated or unsaturated straight-chain or branched chain alkyl).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a polycarbonate resin molding material containing an aromatic dihydroxy compound as a main monomer, and is a polycarbonate resin with excellent moldability and mold release properties and little coloring. This invention relates to resin molding materials.

[Conventional technology and its problems]

In order to improve the mold releasability of polycarbonate resin, methods of adding higher fatty acid esters, wax, liquid paraffin, etc. are known. Considerable improvements can be made using these methods, but recently polycarbonate resins or thermoplastic resin molding materials based on polycarbonate resins have superior characteristics such as transparency, heat resistance, hydrolysis resistance, and dimensional stability. Taking advantage of this, it has come to be widely used in lenses, optical discs, and information disc materials, and along with this, improvements in thermal stability and mold release properties have become important issues.

In particular, optical discs, lenses, etc. are manufactured by injection molding, but when releasing the mold from the mold, if the mold release resistance is high, it can cause warping of the molded product and optical distortion, so it is necessary to use a mold release agent. It is. Particularly in the case of optical discs, it is necessary to accurately transfer the irregularities of 1- or less on the stamper, and this is largely dependent on the performance of the mold release agent.

Paraffin, silicone oil, fatty acids, fatty acid esters, fatty acid partial esters (particularly fatty acid monoglycerides), and the like are conventionally known as mold release agents for polycarbonate resins. Among these, fatty acids and fatty acid monoglycerides have excellent mold release properties when used in small amounts, but these have the effect of accelerating the thermal decomposition of polycarbonate resin, and may color the polycarbonate resin or significantly reduce its molecular weight. It may be reduced.

Therefore, the amount of fatty acid or fatty acid monoglyceride used is preferably 0.05 part by weight or less, particularly 0.01 part by weight or less, based on 100 parts by weight of the polycarbonate resin.

However, with this amount added, the mold releasability is insufficient.

In addition, paraffin, silicone oil, fatty acid ester, etc. have insufficient mold release effect, and polycarbonate resin 1
Although it is preferable to add 0.2 parts by weight or more to 0.00 parts by weight, such an addition amount has the disadvantage that flow marks are likely to occur on the surface of the molded product.

[Problem that the invention seeks to solve]

The present invention has excellent moldability, particularly mold releasability and transferability, and
The object of the present invention is to provide a polycarbonate resin molding material that has excellent heat resistance and exhibits little molecular weight reduction and coloring.

[Means for solving problems]

The present invention is an optical molding material comprising 0.001 to 0.5 parts by weight of α-monoalkylglyceryl ether represented by the following general formula (1) per 100 parts by weight of aromatic polycarbonate resin.

General formula (1): RO-CH2Cl(OH)CH,
(041) ... (1) (R in the formula has 8 to 8 carbon atoms
22 saturated or unsaturated straight or branched alkyl groups).

The configuration of the present invention will be explained below.

The polycarbonate resin of the present invention is a homo- or copolycarbonate resin obtained by the reaction of dihydric phenol with a carbonate precursor such as phosgene or diphenyl carbonate, a further branched resin, or a resin with a long-chain alkyl group introduced at the end. The average molecular weight of things is 12,000 to 30
．． 000; modified polycarbonate resin obtained by using bisphenol or vinylphenol having a carbon-carbon unsaturated double bond as a comonomer or terminal capper, grafted with styrene, etc., and terephthalic acid as part of the phosgene. Examples of materials that can be used include those that use chloride or isophthalic acid chloride and partially have an ester bond, or those that are obtained by graft polymerizing a polycarbonate resin to modified polystyrene that uses a phenolic hydroxyl group as a comonomer. . In addition to optical molding materials, we also use reinforced resin compositions made by compositely reinforcing polycarbonate resin with glass fibers, carbon fibers, PTFE, etc., ABS resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, PMMA resins, etc. It can also be used as an effective mold release agent for resin compositions.

Here, as the dihydric phenol, 2.2-bis(4-
hydroxyphenyl)propane (=bisphenol A)
, bis(4-hydroxyphenyl)methane, 1,2-bis(4-hydroxyphenyl)ethane, 2,2-bis(
4-hydroxyphenyl)butane, 1,1-bis(4-
hydroxyphenyl)-1-phenylmethane, ■.

1-his(4-hydroxyphenyl-1,1-diphenyl)methane, 1. l-bis(4-hydroxyphenyl)
Examples include cyclohexane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, and those in which these phenyl groups are substituted with lower alkyl groups or halogen atoms. In particular, bisphenol A is the most representative.

The α-monoalkyl glyceryl ether of the present invention is a compound represented by the above general formula (1), and has 8 to 22 carbon atoms.
It has a primary, secondary or tertiary alkyl group. This α-monoalkylglyceryl ether is produced by synthesizing alkylglycidyl ether from alcohol and shrimp halohydrin and hydrolyzing it as shown in the following formula; U'' During this hydrolysis, the target α-monoalkylglyceryl Since polymers other than ether may be generated as by-products and the yield of the product may be reduced, prior to hydrolysis, glycidyl ether is reacted with a carbonyl compound to form 4-alkoxymethyl-1,3-dioxolane. It is generally produced by hydrolyzing to a higher purity.

Specifically, n-octylglyceryl ether, n-decylglyceryl ether, laurylglyceryl ether,
Those with straight chain fatty chains such as myristylglyceryl ether, balmitylglyceryl ether, stearylglyceryl ether, alaxylglyceryl ether, behenylcryceryl ether, oleylcryceryl ether: 2-ethylhexylglyceryl ether, 2-hexyldecyl Examples include those having a branched fatty acid such as glyceryl ether, tert-octylglyceryl ether, and tert-dodecylglyceryl ether.

Among these, particularly preferred compounds are valmitylglyceryl ether, stearylglyceryl ether, and behenylglyceryl ether.

The α-monoalkyl glyceryl ether of component (2) is
Like partial esters of polyhydric alcohols having hydroxyl groups in their molecular chains, they provide good mold release properties when added in small amounts, but they have higher heat resistance and less coloring than partial esters of fatty acids. The addition amount is preferably 0.001 to 0.5 parts by weight, and 0.00 parts by weight per 100 parts by weight of the polycarbonate resin.
If it is used in an amount less than 1 part by weight, the effect is small, and if it is used in an amount exceeding 0.5 part by weight, hydrolyzability becomes high, which is not preferable.

Furthermore, in the present invention, the above-described mold release agent (1) is blended as an essential component. Acids, phosphite esters, hindered phenol antioxidants, colorants, ultraviolet absorbers, and the like can be used. These additives are generally mixed into a polycarbonate resin material and then melted and extruded using an extruder, or they can be mixed by adding and mixing into a polycarbonate resin solution and then distilling off the solvent to take out the polycarbonate resin. I can do it.

〔Example〕

The present invention will be explained below with reference to Examples.

In addition, %, parts, etc. in Examples etc. are based on weight unless otherwise specified, and the measurement method was as follows.

Measurement of mold release force.

7.8 oz injection molding machine (manufactured by Mitsubishi Heavy Industries ■, 5
15-150 MST type), resin temperature 280℃,
A molded product in the shape of a pot (bottom inner diameter 60 mm, upper inner diameter 70 mm, depth 70 mm, wall thickness 3ffII11) was molded at a mold temperature of 80°C and an internal mold pressure of 800 to 805 kg/cnf.
The resistance value when this molded product is released from the mold is read by a pressure sensor attached to an ejector pin.

Measurement of molecular weight changes.

The pellets are dried at 120° C. for 4 hours, and approximately 2 g is placed in a test tube and heated at 370° C. for 20 minutes + under a stream of N2. Changes in molecular weight before and after heating are measured using a flow tester (manufactured by @Kinsei Seisakusho,
Temperature 280℃, load 160kg/ciI, orifice 1
mmφxlQmmL) was used as a guideline for molecular weight change.

Incidentally, the smaller the change in Q value before and after heating, the smaller the molecular weight change, and the better the thermal stability.

Measurement of APHA.

4.0g of pellets dried at 120°C for 4 hours and 4g of pellets) were placed in a test tube at 370°C for 20 minutes.

The purified methylene chloride was dissolved in each heated under N2 stream to make a 25rnl solution, and this solution was visually compared with the APHA standard solution.
It depends on how you calculate the number.

The A P IIA standard solution is made by dissolving 1.245 g of potassium chloroplatinate (K2PtCl4) reagent special grade and 1.000 g of cobalt chloride (COCl, .6H20) reagent special grade in 100 d of hydrochloric acid, and adding distilled water to make 100 g. ml
This is used as the standard stock solution of APHA=500, and the following method is used to dilute this to prepare the nuclear APIIA standard solution.

Examples 1 to 5 and Comparative Examples 1 to 7 Caustic soda aqueous solution of bisphenol A and methylene chloride (
=MC) was stirred at 20°C while phosgene was introduced.

Next, p-tert-butylphenol and triethylamine were added, and the mixture was reacted for 1 hour with strong stirring, after which a methylene chloride solution of the reaction product mixture was separated and washed repeatedly with water.

Add 2 parts of rhohebutane (=nH) to 100 parts by volume of this solution.
5 parts by volume were added and mixed, the mixed solution was dropped into warm water, and then the temperature was raised to 100°C and the solvent was distilled off to obtain a slurry of polycarbonate powder.

This powder was filtered out and dried at 120°C for 8 hours to obtain polycarbonate with a viscosity average molecular weight of 15.000.

This polycarbonate powder was mixed with 0.005 part of tris(2,4-di-t-butylphenyl) phosphite as a mold release agent and stabilizer listed in Table 1 to give a powder of 250 to 27
A molding material was obtained by extrusion and pelletizing at a resin temperature of 0°C.

Table 1 shows the results of measurements of mold release resistance, molecular weight changes, and long-term moisture resistance tests using the above pellets.

Sil: Shimenal Kosunro Dried 7n.

[Operation and effects of the invention]

As mentioned above, when compared with conventionally known mold release agents, the polycarbonate resin composition of the present invention exhibits less change in molecular weight and less coloring upon heating than, for example, monoglycerides of fatty acids, and
It has better mold release properties than fatty acid esters and silicone oils.

As described above, it has excellent heat resistance and mold releasability, so it is useful as a transparent resin or resin composition as an optical molding material, and it is also a composition that is more preferable for general use due to its thermal stability and mold releasability. It is easy to understand that it is something that can be provided.

Patent applicant: Mitsubishi Gas Chemical Co., Ltd.

Claims (1)

[Scope of Claims] A polycarbonate resin molding material comprising 0.001 to 0.5 parts by weight of α-monoalkylglyceryl ether represented by the following general formula (1) per 100 parts by weight of aromatic polycarbonate resin. General formula (1): RO-CH_2CH(OH)CH_2(
OH)...(1) (R in the formula represents a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms).